Classifications

• • G—PHYSICS
  • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
  • G03C—PHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
  • G03C1/00—Photosensitive materials
  • G03C1/52—Compositions containing diazo compounds as photosensitive substances
  • G03C1/60—Compositions containing diazo compounds as photosensitive substances with macromolecular additives
• • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
  • Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y10S8/00—Bleaching and dyeing; fluid treatment and chemical modification of textiles and fibers
  • Y10S8/916—Natural fiber dyeing
  • Y10S8/919—Paper

Definitions

• the invention relates to two-component diazotype paper containing a light-sensitive diazo compound and an azo component, which upon development form together an azo dyestuff which carries at least one group enhancing the solubility of the azo dyestulf in water.
• Such diazotype papers are known.
• a diazo compound derived from a p-phenylene diamine and a readily water-soluble azo component of the naphthol type, such as 2,3-dihydroxy naphthalene 6-sulphonic acid, 2,7- dihydroxy naphthalene 3,6-disulphonic acid, 1,8-dihydroxy naphthalene 4-sulphonic acid, Z-hydroxy naphthalene 6-sulphonic acid, Z-hydroxy naphthalene 3,6-disulphonic acid, or of the phenol type, such as resorcinol sulphonic acids, phloroglucinol carboxylic acid, l-acetylacetamino benzene 3-sulphonic acid, and 1-(4'-sulphophenyl) 3-methyl pyrazolone-( Upon coupling, these combinations yield water-soluble azo dyestuffs.
• diazo compounds with one or more substituents enhancing the solubility in water such as a diazo compound with a dialkylamino group in para-position, in which one or both of the alkyl radicals carry a hydroxyl group, such as p-diazo N-ethyl N-hydroxyethylaniline, or a diazonaphthol sulphonic acid, such as 2-diazo l-naphthol 5-sulphonic acid and l-diazo 2-naphthol 4-sulphonic acid.
• a diazo compound with a dialkylamino group in para-position in which one or both of the alkyl radicals carry a hydroxyl group, such as p-diazo N-ethyl N-hydroxyethylaniline, or a diazonaphthol sulphonic acid, such as 2-diazo l-naphthol 5-sulphonic acid and l-diazo 2-napht
• diazo compounds yield water-soluble azo dyestuffs upon coupling with a polyvalent phenol, such as resorcinol and phloroglucinol, or a naphthol such as 2,3-dihydroxynaphthalene.
• a polyvalent phenol such as resorcinol and phloroglucinol
• a naphthol such as 2,3-dihydroxynaphthalene
• Two-component diazotype paper which contains a diazo compound and/ or an azo component with a group enhancing the solubility in water, yields copies the azo dyestufI' image of which has insuificient water-fastness, i.e., when the copies get wet, the azo dyestufi image will bleed owing to the solubility of the azo dyestuif in water.
• the azo dyestuff image then not only loses its sharp contours, but moreover the dissolving azo dyestuif will dirty the water colour.
• agents have been suggested in the literature for improving the water-fastness of the azo dyestuif image in copies made on two-component diazotype paper which contains a diazo compound and/or an azo component with a group enhancing the solubility in water.
• these agents are substances containing a basic nitrogen atom, such as: aryl derivatives of guanidine and biguanidine (United States patent specification No. 1,807,761), amines, such as cyclohexylamine, dicyclohexylamine, morpholine, amylamine, glycine, quinoline, and ethylene diamine (United States patent specification No.
• a suitable substance is, for example, a quaternary ammonium base obtained by peralkylation of 5,5'-methylene bis-(Z-methyl benzimidazole) (French patent specification No. 803,821
• both the said quaternary ammonium base and the said condensation products often form precipitates when added to aqueous sensitizing liquids which contain a diazo compound or an azo component with a group enhancing the solubility in water. In such cases these compounds have to be applied, in the production of the diazotype material, in a separate treatment before or after sensitization.
• two-component diazotype paper containing a light-sensitive diazo compound and azo component, which upon development form together an azo dyestuff with at least one group enhancing the solubility in water, the said paper further containing, as an agent for improving the water-fastness of the azo dyestuif, a compound selected from Z-hydroxymethyl 1',2,4,5-naphthimidazole, 2-hydroxyethyl 1,2',4,5-naphthimidazo1e, and l,2',4,5-naphthimidazole with a hydrogen atom, a methyl, a hydroxymethyl, or a hydroxyethyl group in Z-position and a hydroxyl group in 5', 6', or 7-position.
• Such diazotype paper yields copies the azo dyestulf image of which has excellent water-fastness, in many cases better than the azo dyestutf image of copies on corresponding diazotype paper containing a comparable quantity of the best of the previously known agents.
• the said imidazoles are all sufiiciently soluble in the aqueous sensitizing liquids commonly used for making two-component diazotype paper. Consequently they need not be applied in or on the diazotype paper in a separate treatment, before or after sensitization. In most cases they are applied as salts of strong acids, such as hydrochloric acid.
• a quantity of one or more of the said imidazoles varying between 1 mol and 2 mols of imidazole per mol of diazo compound is applied in the diazo-type paper according to the invention. Often smaller quantities will suflice, for example when the imidazoles are applied in combination with one or more of the known agents. If, however, exclusively imidazole is used and if the azo dyestuff contains more than one group enhancing the solubility in water, a quantity of imidazole which is larger than 2 mols per mol of diazo compound may be required. Such a larger quantity, however, does not have a detrimental effect on the development of the copies, this being in contrast with, for instance, the effect of an equally active quantity of one of the condensation products of dicyanodiamide.
• the required quantity of imidazole moreover is always considerably smaller than an equally active quantity of those condensation products.
• the agents for improving the water-fastness, applied in the diazotype paper according to the present invention are all very effective. Nevertheless there are differences in activity among them.
• the most active agents are the 1,2,4,S-naphthimidazoles the naphthalene nucleus of which carries a hydroxyl group in 6', or 7-position, such as 5'-hydroxy 1,2,4,S-naphthimidazole, 5-hydroxy 2-methyl 1,2',4,S-naphthimidazole, 5'-hydroxy 2-hydroxymethyl 1',2',4,S-naphthimidazole, 5'-hydroxy Z-ahydroxyethyl l,2,4,S-naphthimidazole, 5-hydroxy 2-[3- hydroxyethyl 1,2,4,5-naphthimidazole, 6-hydroxy 1,2,- 4,5-naphthimidazole, 6-hydroxy 2-methyl 1,2,4,5-naphthimidazole, 6'-hydroxy 2-hydroxymethyl 1',2,4,5-na
• the said particles have a much smaller detrimental effect, if any, on the possibility of writing with ink on the copies, while their favourable influence on the density of the azo dye-stuff image and the uniformity of the light-sensitive layer is maintained.
• the said naphthimidazoles moreover will sometimes favourably affect the adhesion of such particles with colloidal dimensions to the surface of the copies.
• the hydroxynaphthimidazole compounds are able to couple with diazo compounds to form azo dyestuffs, mostly red-coloured ones. Their coupling activity, however, is small.
• an azo component which is sufiiciently active and is used in a quantity which is large enough to convert all the diazo molecules into azo dyestuff, so that no azo dyestulf is formed from the added hydroxynaphthimidazole.
• Diazotype material containing 6'- or 7-hydroxy 1',2,- 4,5-naphthimidazole is known.
• 6-hydroxy 1',2',4,5-naphthimidazole and 7-hydroxy 1',2,4,5-naphthimidazole have been suggested as azo components for the diazotype process. They couple slowly to form more or less red azo dyestuffs.
• no other azo components besides these naphthimidazoles are applied.
• United States patent specification No. 2,542,716 describes two-component diazotype material which contains 7'-hydroxy 1,2',4,5-naphthimidazole in combination with a very small quantity of a more actively coupling azo component.
• the latter may be LS-dihydroxy naphthalene 4-sulfphonic acid.
• Per gram molecule of diazo compound only gram-molecule of it is present. Consequently the azo dyestutf formation in this diazotype material, at least in the poorly exposed and non-exposed portions, is not essentially determined by the 1,8-dihydroxynaphthalene 4-sulphonic acid, but by the 7-hydroxy 1,2,4,S-naphthimidazole.
• the very small quantity of azo dyestufl ?
• Example I White base-paper for the diazotype process of weight g./m. is precoated with approximately 10 g./m. of a dispersion of 30 g. of Aerosil (colloidal silica) in 1000 cm. of water and dried.
• Aerosil colloidal silica
• the surface thus treated is sensitized (at room temperature) with a solution of 16 g. of p-diethylamino benzene diazonium chloride, zinc chloride double salt 40 g. of 2,3-dihydroxy naphthalene 6-sulphonic acid sodium salt 30 ml. of Vinnapas H.60 (polyvinyl acetate emulsion) 20 g. of 7'-hydroxy 1,2,4,5-naphthimidazole HCl-salt in 1000 cm. of water and dried.
• the light-sensitive side of a sheet of the diazotype paper thus obtained is covered with a tracing with broad nomines having good absorption for ultraviolet light (e.g., black lines) and then exposed via the tracing until, underneath the blank portions of the tracing, the diazo compound has bleached out completely. After this the image is developed in ammonia vapour.
• a tracing with broad nomines having good absorption for ultraviolet light e.g., black lines
• the diazotype copy thus made shows a dense blue image on a clear white background.
• the silica particles adhere well to the surface of the copy. It is possible to write or draw on the surface of the copy with various inks without encountering difficulties in the way of ink-feathering.
• Example II White base-paper for the diazotype process of weight 80 g./m. is sensitized with a solution of the following, applied at 18 C.:
• a sheet of the highly light-sensitive diazotype paper thus prepared is irnagewise exposed and developed as described 1n Example I.
• the copy obtained shows a dense neutral black azo dyestufi image on a white background, which shows hardly any bleeding when the copy gets wet, this being in striking contrast with the azo dyestuif image of a copy on corresponding diazotype paper which does not contain the imidazole.
• Example III White base-paper for the diazotype process of weight 80 g./m. is sensitized with a solution of the following, applied at 18 C.:
• a sheet of the diazotype paper thus made is irnagewise exposed and developed as described in Example I.
• the copy obtained which shows a violet image on a white background, has considerably better water-fastness than a copy on corresponding diazotype paper without the said imidazole.
• Example IV White base-paper for the diazotype process of. weight g./m. is sensitized with a solution of the following, applied at room temperature:
• zinc chloride double salt 20 g. of 2-hydroxynaphthalene 6-sulphonic acid sodium salt 30 g. of citric acid 30 g. of thiourea 40 g. of zinc chloride 50 g. of N.N'-dimethylurea 20 g. of 6'-hydroxy 1,2',4,5-naphthimidazole HCl-salt 3O cm. of Vinnapas H.60.
• a sheet of this diazotype paper is irnagewise exposed and developed as described in Example I.
• the copy shows a dense brown azo dyestulf image which exhibits hardly any bleeding when it gets wet.
• the copy can be properly painted with water colour.
• the azo dyestuff of the image mixes with the Water colour.
• Example V Tracing paper is sensitized with a solution of the following, applied at 20 C.: 30 g. of p-N-2'-hydroxyethyl N-ethylamino benzene diazonium chloride, zinc chloride double salt 30 g. of tartaric acid 10 g. of boric acid 30 g. of thiourea 30 g. of zinc chloride 30 g. of resorcinol 30 g. of 2-methy1 7'-hydroxy 1',2',4,5-naphthimidazole 250 cm. of ethanol in 750 cm. of water and then dried.
• the azo dyestutf image of a copy on corresponding diazotype material, but without imidazole, on the contrary has poor water-fastness.
• the transparent copies obtained according to this example are very suitable as intermediate originals for making further copies on photoprinting material.
• Example VI White base-paper for the diazotype process of weight 80 g./m. is treated on the side to be sensitized with a solution containing the following, applied at 18 C.:
• the paper thus precoated is sensitized with the sensitizing solution of Example I, from which the 7-hydroxy 1,2',4,5-naphthimidazole HCl-salt, however, has been omitted.
• a sheet of the diazotype paper is then imagewise exposed and developed in ammonia vapour.
• the azo dyestuff image of the diazotype copy is a neutral blue and has excellent water-fastness.
• Two-component diazotype paper comprising a paper support sensitized thereover with a light-sensitive compo sition comprising a light-sensitive diazo compound and an azo coupling component which couples with said compound more actively than does any of 2-hydroxymethy1 1',2',4,5-naphthimidazole, 2-hydroxyethyl 1',2,4,5-naphthimidazole and 1',2',4,S-naphthimidazoles having a hydroxyl group in one of the 5', 6', and 7 positions on the naphthalene nucleus and which upon coupling with said compound forms therewith a water soluble azo dyestufi that tends to bleed when wetted by water, said support carrying thereover in intimate contact with said diazo compound and said azo coupling component an agent to enhance the water-fastness of said dyestuff, selected from the group consisting of Z-hydroxymethyl 1',2,4,5-naphthimidazole,
• 1,2',4,5-naphthimidazoles having in the 2-position on the imidazole nucleus a constituent selected from the class consisting of a hydrogen atom and methyl, hydroxy-methyl and hydroxy-ethyl groups and having a hydroxyl group in one of the 5, 6 and 7 positions on the naphthalene nucleus,
• said azo coupling component having a coupling activity, and being present in a concentration exceeding that which is stoichiometric to the quantity of said diazo compound present, suflicient that upon development of said paper said component will couple with substantially all the diazo compound therein to the exclusion of any substantial coupling of said agent therewith, said agent being present in a quantity sufficient to render substantially non-bleeding, when wetted by water, an image of said dyestuff formed on said support by imagewise exposure and development of said paper.
• Two-component diazotype paper according to claim 1, said light-sensitive composition containing said agent in admixture with said diazo compound and said azo coupling component.
• Two-component diazotype paper according to claim 1 said support carrying thereover in intimate contact with said light-sensitive composition a coating of inorganic oxide particles of colloidal size.
• Two-component diazotype paper according to claim 3 said colloidal particles and said agent being in admixture with said diazo compound and said azo coupling component as parts of said light-sensitive composition.
• Two-component diazotype paper according to claim 3 said coating covering a surface of said support and being overlaid by said light-sensitive composition, said composition containing said agent in admixture with said diazo compound and said azo coupling component.
• Two-component diazotype paper according to claim 1 said agent being carried on a surface of said support in a sub-layer overlaid by said light-sensitive composition.
• Two-component diazotype paper according to claim 1 said light-sensitive composition containing said agent in admixture with said diazo compound and said azo coupling component, at a concentration of about 1 to 2 mols of said agent per mol of said diazo compound.
• Two-component diazotype paper comprising a paper support sensitized thereover with a light-sensitive composition comprising a light-sensitive diazo compound and an azo coupling component which couples with said compound more actively than does any of 2-hydroxymethyl 1,2,4,5-naphthimidazole, 2-hydroxyethyl 1',2,4,5-naphthimidazole and 1,2,4,S-naphthimidazoles having a hydroxyl group in one of the 5, 6 and 7 positions on the naphthalene nucleus and which upon coupling with said compound forms therewith a water soluble azo dyestuif that tends to bleed when wetted by water, said support carrying thereover in intimate contact with said diazo compound and said azo coupling component a quantity of 5 hydroxy-1,2,4,5-naphthimidazole, said azo coupling component having a coupling activity, and being present in a concentration exceeding that which is stoichiometric to the quantity of said diazo compound present, sufiicient
• diazo compound being a diazo derivative of a p-phenylene diamine
• said azo coupling component being selected from the group consisting of hydroxy-naphthalene sulfonic acids
• Two-component diazotype material according to claim 1, said diazo compound being selected from the group consisting of p-N-alkyl-N-hydroxyalkyl amino and p-dihydroxyalkyl amino-benzene diazo compounds and diazonaphthol sulfonic acid compounds, said azo coupling component being a naphthol.
• a sensitizing composition for the manufacture of two-component diazotype paper comprising a mixture of a light-sensitive diazo compound, an azo coupling component'which couples with said compound more actively than does any of 2-hydroxymethyl 1,2,4,5-naphthimidazole, Z-hydroxyethyl 1',2',4,5-naphthimidazole and 1,2, 4,5-naphthimidazoles having a hydroxyl group in one of the 5', 6' and 7' positions on the naphthalene nucleus and which upon coupling with said compound forms therewith a Water soluble azo dyestuif that tends to bleed when wetted by water, and, per mol of said diazo compound, about 1 to 2 mols of an agent to enhance the water-fastness of said dyestult, selected from the group consisting of 2-hydroxymethyl 1',2,4,S-naphthimidazole,
• 1',2',4,5-naphthimidazoles having in the 2-position on the imidazole nucleus a constituent selected from the class consisting of a hydrogen atom and methyl, hydroxy-methyl and hydroxy-ethyl groups and having a hydroxyl group in one of the 5', 6' and 7' positions on the naphthalene nucleus,
• said azo coupling component having a coupling activity, and being present in a concentration exceeding that which is stoichiometric to the quantity of said diazo compound present, sufiicient that under coupling conditions it w ll couple with substantially all the diazo compound in said composition to the exclusion of any substantial coupling of said agent therewith.
• Two-component diazotype paper comprising a paper support sensitized thereover with a light-sensitive composition comprising a light-sensitive diazo compound and an azo coupling component which couples with said compound more actively than do any of Z-hydroxymethyl 1',2',4,5-naphthimidazole, Z-hydroxyethyl 1',2', 4,5-naphthimidazole and 1',2,4,S-naphthimidazoles having a hydroxyl group in one of the 5', 6 and 7' positions on the naphthalene nucleus, and which upon coupling with said compound forms therewith a water soluble azo dyestuff that tends to bleed when wetted by water, said support carrying thereover in intimate contact with said diazo compound and said azo coupling component a quantity of 6-hydroxy-1,2,4,5-naphthimidazole, said azo coupling component having a coupling activity, and being present in a concentration exceeding that which is stoichiometric to the
• Two-component diazotype paper comprising a paper support sensitized thereover with a light-sensitive composition comprising a light-sensitive diazo compound and an azo coupling component which couples with said compound more actively than do any of 2-hydroxymethyl 1',2,4,5-naphthimidazole 2-hydroxyethyl 1,2',4,5-naphthimidazole and 1',2',4,5-naphthimidazoles having a hydroxyl group in one of the 5', 6' and 7' positions on the naphthalene nucleus and which upon coupling with said compound forms therewith a water soluble azo dyestuff that tends to bleed when wetted by water, said support carrying thereover in intimate contact with said diazo compound and said azo coupling component a quantity of 7'-hydroxy-1',2',4,5-naphthimidazole, said azo coupling component having a coupling activity, and being present in a concentration exceeding that which is stoichiometric to the quantity of
• Two-component diazotype paper comprising a paper support sensitized thereover with a light-sensitive composition comprising a light-sensitive diazo compound and an azo coupling component which couples with said compound more actively than do any of 2-hydroxymethyl l',2',4,5-naphthimidazole, Z-hydroxyethyl 1',2',4,5-naphthimidazole and 1',2',4,5-naphthimidazoles having a hydroxyl group in one of the 5', 6' and 7 positions on the naphthalene nucleus and which upon coupling with said compound forms therewith a water soluble azo dyestuif that tends to bleed when wetted by water, said support carrying thereover in intimate contact with said diazo compound and said azo coupling component a quantity of 2-methyl-7'-hydroxy 1',2',4,5 naphthimidazole, said azo coupling component having a coupling activity, and being present in a concentration exceeding that which is stoichi
• Two-component diazotype material according to claim 1, said diazo compound being selected from the group consisting of p-N-alkyl-N-hydroxyalkyl amino and p-dihydroxyalkyl amino benzene diazo compounds and diazonaphthol sulfonic acid compounds, said azo coupling component being a polyvalent phenol.

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  • NL NL254486D patent/NL254486A/xx unknown
  • BE BE606539D patent/BE606539A/xx unknown
• 1961
  • 1961-07-18 GB GB26062/61A patent/GB953908A/en not_active Expired
  • 1961-07-20 DE DE19611422829D patent/DE1422829B1/de active Pending
  • 1961-07-24 US US125941A patent/US3140181A/en not_active Expired - Lifetime
  • 1961-08-02 ES ES0269535A patent/ES269535A1/es not_active Expired

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